



Patented Oct. 11, 1949 2,484,528 FLUOROMETHYLTRIAZINES George W. Rigby,

signor to E. I. du Wilmington,

Del., a corporation N Drawing. Application May 15, 1945,

Serial No. 6 Claims. (Cl. 260-248) This invention relates to the preparation of fluorinated organic compounds and to new organic fluorine compounds. More particularly, this invention relates to fluoromethyl triazines and a process for the preparation of these compounds.

This application is a continuation in part of copending application Serial No. 484,302, filed April 23, 1943, now Patent No. 2,409,315, by myself and Herman E. Schroeder.

This invention has as an object a new class of chemical compounds, namely 2,4,6-tris-(fluoromethyl) triazines. A further object is 2A.,6-tris- (monofluoromonochloromethyl) triazine. A still further object is 2,4,6-tris-(difluoromethyl)triazine. A still further object is the provision of a process for obtaining said fluoromethyl triazines. Additional objects will become apparent from an examination of the following description and claims.

These and other objects and advantages are accomplished according to the herein described invention, which comprises reacting ammonia with a polyfluoroethylene containing at least three fluorine atoms. The prefix (poly) as used herein and in the appended claims refers to the number of fluorine atoms present in the fluoroethylene and not to polymeric materials.

The reaction of this invention may be illustrated by the following equation:

wherein X is a member of the group consisting of hydrogen and halogen atoms.

The following examples, in which proportions are in parts by weight unless otherwise specified, are given for illustrative purposes and are not intended to place any restrictions on the herein described invention.

Example I Brandywine Hundred, Del., as-

Pont de Nemours & Company,

of Delaware the ammonium fluoride, which was formed in the reaction, by extraction with ether. The ether extract was fractionally distilled to recover 22 g. of 2,4,6-tris- (difluoromethyl) triazine which boiled at 72-73 C./9 mm. Calcd. for (CF2HCN)32 F, 49.4%; molecular weight, 231; molecular refractivity, 35.6. Found: N, 17.9%; F, 47.0%; molecular weight, 213; molecular refractivity, 35.1.

Upon hydrolysis of the 2,4,6-tris- (difluoromethyl) triazine in neutral, acid or alkaline aqueous solution, difluoroacetic acid was obtained. I

Example II A silver-lined high-pressure reactor was swept with nitrogen and charged with 0.2 part of cupric acetate and 72 parts of anhydrous ether. The. tube was closed, chilled, evacuated and'further charged with 25 parts of anhydrous ammonia and 58 parts of chlorotrifluoroethylene. The reactor was allowed to warm gradually from about C. to room temperature with occasional shaking. After four hours or when the reactor had warmed to room temperature, the reactor was opened and the product discharged. Fractionation of 5.5 parts of 2,4,6-tris-(chlorofluoromethyl)triazine boiling at -96 C. at 3 mm. Calcd. for (CHC1FCN)3: N, 15.0%; F, 20.3%; C, 25.7%. Found: N, 14.3%; F,21.6%; C, 26.5%. 1

While the process of this invention has been illustrated with particular reference to the reaction of ammonia with tetrafluoroethylene and chlorotrifluoroethylene, it is to be understood that it is broadly applicable to all polyfluoroethylenes containing at least three fluorine atoms, 1. e., to all compounds having the general formula CF2=CFX, wherein X is a member of the group consisting of hydrogen and halogen atoms. Included among examples of said polyfluoroethylenes are: trifluorobromoethylene, trifluoroethylene, trifluorochloroethylene and tetrafluoroethylene. The tetrahaloethylenes react more readily than trifluoroethylene and tetrafluoroethylene is particularly preferred as it reacts the most readily.

The method of carrying out the reaction may vary to some extent with the different polyfiuoroethylenes, but the usual procedure consists in charging the polyfluoroethylene and ammonia under anhydrous conditions into the reactor and permitting the reaction to take place at temperatures below C. At higher temperatures the reaction proceeds vigorously and may result in the resultant product yielded explosion. In general, temperatures within the range of 30 C. to 50 C. are employed. It is preferable to carry out the reaction in the water, the triazine may bydrolyze to form the fiuoroacetic acidas indicated in Example I.

It is usually desirable to ,use a molar excess of ammonia rather than the ethylene. With the more reactive fluoroethylenes, such as tetrafluoroethylene/it isn'ften desirable to employ an organic solvent, such as diethyl ether, dioxane or benzene.

The novel products of this invention are 2,4,6-

tris-.(fluoromethyl)triazines, i. e., :compounds having .the general formula:

N EXEC-53 O-O-FXH wherein X is .a member of the group consisting of hydrogen and halogenatoms. Included among specific examples .of saidproducts are: L2,4,6-tris- (monofluoromonobromomethyl) triazine, 2,4,6- tris (monofluoromethyl)triazine, 2,4,6 tris- (monofluoromonochloromethyl) triazine and 2,4,6- trisdifiuoromethyl) triazine.

The products of Various commercial CFXH member of the group consisting chlorine, bromine and fluorine wherein X is a of hydrogen, atoms.

2. The chemical compound 2,4;6-tr1's-(difiuoromethyl) triazine having'the formula ;3. .The chemical compound 2,4,6-tris-(monomore (expensive fluorochloromonofiuoromethyl) triazine having the formula N Ho1Fo o \COFOIH J 1t 0 F 01H 41. The process for obtaining a 2,4,6-tris- (fluoromethyl) triazine having the general formula therefrom the s oformed triazine.

'5. 'I-he=process-for obtaining 2,4,-'6-tris--(difluoromethyl) triazine having the formula l-F211 which comprises reacting ammonia with trifiuoroethylene by contacting said ammonia with therefrom the so-formeol triazine.

6. The process for obtaining 2,4,6-tris- (monochloromonofluoromethyl) triazine having the formula Hem o-(l/ fpcn 0111 l CFGIH GEORGE W. RIGBY.

REFERENCES CITED The following references are of file of this patent:

FOREIGN PATENTS record the Number Country Date 1682;391 Germany 1,939 ..699,4,93 Germany 1940 117,464 Australia .-Sept..1,1:943 

